β Crystalline polypropylenes

ABSTRACT

A composition containing (1) a crystalline polypropylene resin and (2) one or more β-nucleating agents of the formula (I), wherein R 1 , R 2  and R 3 , independently of one another, are C 1 -C 20 alkyl, C 2 -Calkyl substituted by C 1 -C 10 alkylamino, di(C 1 -C 10 alkyl)amino, C 1 -C 10 alkyloxy or hydroxy; C 3 -C 20 alkenyl, C 5 -C 12 cycloalkyl, C 5 -C 12 Cycloalkyl substituted by 1, 2 or 3 C 1 -C 10 alkyl; cyclohexylmethyl; cyclohexylmethyl substituted by 1, 2 or 3 C 1 -C 10 alkyl; C 5 -C 9 cycloalkenyl, C 5 -C 9 cycloalkenyl substituted by 1, 2 or 3 C 1 -C 10 alkyl; phenyl substituted by 1, 2 or 3 radicals selected from the group consisting of C 1 -C 10 -oalkyl, C 1 -C 10 alkyloxy, hydroxy, halogen, trihalogenmethyl, trihalogenmethoxy, benzoyl, phenylamino, acylamino and phenylazo; C 7 -C 9 phenylalkyl, C 7 -C 9 phenylalkyl which is substituted on the phenyl by 1, 2 or 3 radicals selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 10 alkoxy and hydroxy; naphthyl, naphthyl substituted by C 1 C 10 alkyl, adamantyl, or a 5 to 6 membered heterocyclic group; characterized in that the polypropylene resin has a content of β-form crystals of at least 10% calculated by means of the following equation β-form crystal content (%)=100×P β1 ,/(P a1 +P a2 +P a3 +P β1 ) where P a1  to P a3  are respective peak heights (maxima) of the a-form and P β1  is a peak height (maximum) of the β-form determined by wide angle X-ray scattering.

The present invention relates to a composition containing a crystallinepolypropylene resin and one or more specific trimesic acid derivativescapable of acting as a nucleating agent for the formation of theβ-crystal form, to the use of these derivatives as β-nucleating agentsand to articles made from a polypropylene resin containing the β-formcrystals.

It is known that crystalline polypropylene may occur in α, β, γ and δcrystal forms as well as in the smectic crystal form which is formed onquenching of melted polypropylene. The β-crystal form (hereinafterreferred to as “β-form”) differs from the more common α-form which isfound, for instance, in the conventional natural pellets in that it islower in melting point and in density, not to speak of differences inthe mode of crystallization and of fracture, thus being of interest fromapplication points of view.

The β-form of polypropylene is less stable compared with thecorresponding α-form under usual processing conditions. When melts ofpolypropylene are extruded and then cooled the α-form of polypropylenetends to predominate. However, polypropylene containing high contents ofthe β-form can be prepared by the addition of a suitable nucleatingagent which induces the formation of the β-form when the polypropyleneis molten and subsequently cooled.

U.S. Pat. No. 6,235,823 describes the use of diamide compounds asβ-nucleating agents. EP-A-940,431 and JP-A-Hei 06/192,496 disclose theuse of several trimesic acid derivatives as nucleating agents ingeneral, however, without differentiating between the several crystalforms. Not any nucleating agent for polypropylene resins doesnecessarily induce the formation of the β-crystal form.

EP-A-865,914 and EP-A-865,911 describe polyolefin films. Polybutene-1resin compositions are disclosed in EP-A-776,933, and porous stretchedarticles of polypropylene based resin are described in EP-A-632,095.

The present invention relates in particular to a composition containing

-   (1) a crystalline polypropylene resin and-   (2) one or more β-nucleating agents of the formula (I),

wherein

-   R₁, R₂ and R₃, independently of one another, are-   C₁-C₂₀alkyl,-   C₂-C₂₀alkyl substituted by C₁-C₁₀alkylamino, di(C₁-C₁₀alkyl)amino,    C₁-C₁₀alkyloxy or hydroxy;-   C₃-C₂₀alkenyl,-   C₅-C₁₂cycloalkyl,-   C₅-C₁₂cycloalkyl substituted by 1, 2 or 3 C₁-C₁₀alkyl;-   cyclohexylmethyl;-   cyclohexylmethyl substituted by 1, 2 or 3 C₁-C₁₀alkyl;-   C₅-C₉cycloalkenyl,-   C₅-C₉cycloalkenyl substituted by 1, 2 or 3 C₁-C₁₀alkyl;-   phenyl substituted by 1, 2 or 3 radicals selected from the group    consisting of C₁-C₁₀alkyl,-   C₁-C₁₀alkyloxy, hydroxy, halogen, trihalogenmethyl,    trihalogenmethoxy, benzoyl,-   phenylamino, acylamino and phenylazo;-   C₇-C₉phenylalkyl,-   C₇-C₉phenylalkyl which is substituted on the phenyl by 1, 2 or 3    radicals selected from the group consisting of C₁-C₁₀alkyl,    C₁-C₁₀alkoxy and hydroxy;-   naphthyl,-   naphthyl substituted by C₁-C₁₀alkyl;-   adamantyl, or-   a 5 to 6 membered heterocyclic group;

characterized in that the polypropylene resin has a content of β-formcrystals of at least 10%, for example at least 20% or 30% or 40% or 50%or 60% or 70% or 80% or 90% or 95%, calculated by means of the followingequationβ-form crystal content (%)=100×P _(β1)/(P _(α1) +P _(β2) +P _(α3) +P_(β1))where P_(α1) to P_(α3) are respective peak heights (maxima) of theα-form and P_(β1) is a peak height (maximum) of the β-form determined bywide angle X-ray scattering.

P_(β1) is a reflection intensity (height) on (300) plane of β-formcrystal.

P_(α1) is a reflection intensity (height) on (110) plane of α-formcrystal.

P_(α2) is a reflection intensity (height) on (040) plane of α-formcrystal.

P_(α3) is a reflection intensity (height) on (130) plane of α-formcrystal.

The β-form crystal content may be determined as described by A. TurnerJones et al. in Makromol. Chem. 75, 134 (1964) or as described in U.S.Pat. No. 5,491,188.

In the crystalline polypropylene resin, 10% or more of β-form crystalcontent determined by wide angle X-ray scattering has to be found in atleast one direction.

A preferred embodiment of the present invention relates to a compositionwherein the β-form crystals of component (1) are solidified and/orannealed at ambient temperature or at temperatures (T_(s))T _(s) ≦T _(cr)+35° C.

T_(cr) being the recrystallization temperature of the polypropyleneresin (component (1)) without a β-nucleating agent as determined bydifferential scanning calorimetry (DSC) by cooling the moltenpolypropylene resin at a cooling rate of 10 K/min.

Examples of suitable solidifying and/or annealing temperatures T_(s)are:

-   (T_(cr) minus 120° C.) to (T_(cr) plus 35° C.)-   (T_(cr) minus 100° C.) to (T_(cr) plus 35° C.)-   (T_(cr) minus 80° C.) to (T_(cr) plus 35° C.)-   (T_(cr) minus 60° C.) to (T_(cr) plus 35° C.)-   (T_(cr) minus 40° C.) to (T_(cr) plus 35° C.)-   (T_(cr) minus 20° C.) to (T_(cr) plus 35° C.)-   T_(cr) to (T_(cr) plus 35° C.)-   (T_(cr) minus 150° C.) to (T_(cr) minus 100° C.)-   (T_(cr) minus 120° C.) to (T_(cr) minus 80° C.)-   (T_(cr) minus 120° C.) to (T_(cr) minus 60° C.)-   (T_(cr) minus 120° C.) to (T_(cr) minus 40° C.)-   (T_(cr) minus 120° C.) to (T_(cr) minus 20° C.)-   (T_(cr) minus 120° C.) to T_(cr).-   (T_(cr) minus 90° C.) to (T_(cr) minus 80° C.)-   (T_(cr) minus 90° C.) to (T_(cr) minus 60° C.)-   (T_(cr) minus 90° C.) to (T_(cr) minus 40° C.)-   (T_(cr) minus 90° C.) to (T_(cr) minus 20° C.)-   (T_(cr) minus 90° C.) to T_(cr)

The following solidifying and/or annealing temperatures T_(s) arepreferred:

-   (T_(cr) minus 80° C.) to (T_(cr) minus 60° C.)-   (T_(cr) minus 80° C.) to (T_(cr) minus 40° C.)-   (T_(cr) minus 80° C.) to (T_(cr) minus 20° C.)

The following solidifying and/or annealing temperatures T_(s) areparticularly preferred:

-   (T_(cr) minus 120° C.) to (T_(cr) minus 100° C.)-   (T_(cr) minus 110° C.) to (T_(cr) minus 80° C.)-   (T_(cr) minus 110° C.) to (T_(cr) minus 90° C.)-   (T_(cr) minus 80° C.) to (T_(cr) minus 60° C.)-   (T_(cr) minus 40° C.) to (T_(cr) minus 20° C.)-   (T_(cr) minus 60° C.) to (T_(cr) minus 40° C.)-   (T_(cr) minus 20° C.) to (T_(cr) plus 10° C.)-   T_(cr) to (T_(cr) plus 35° C.)-   T_(cr)

Also of interest are:

-   (T_(cr) minus 70° C.) to (T_(cr) plus 20° C.)-   (T_(cr) minus 60° C.) to (T_(cr) plus 10° C.)

Examples of C₁-C₂₀alkyl are methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl,1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methyl-hexyl, n-heptyl,isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl,n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl,nonyl, decyl, undecyl, 1-methyl-undecyl, dodecyl,1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl and eicosyl.

Preferred examples are butyl, octyl and octadecyl.

Examples of C₂-C₂₀alkyl substituted by C₁-C₁₀alkylamino,di(C₁-C₁₀alkyl)amino, C₁-C₁₀alkyloxy or hydroxy are 3-methylaminopropyl,2-dimethylaminoethyl, 2-diethylaminoethyl, 3-dimethylaminopropyl,3-diethylaminopropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-methoxypropyl,3-methoxypropyl, 2-ethoxypropyl, 3-isopropoxypropyl and hydroxyethyl.

Preferred examples are 3-dimethylaminopropyl, 3-methoxypropyl and2-methoxyethyl.

Examples of C₃-C₂₀alkenyl are allyl, 2-methallyl, butenyl, pentenyl,hexenyl and oleyl. The carbon atom in position 1 is preferablysaturated. Particularly preferred examples are allyl and oleyl.

Examples of C₅-C₁₂cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl and cyclododecyl.

Preferred examples are cyclohexyl, cycloheptyl, cyclooctyl andcyclododecyl.

Preferred examples of C₅-C₁₂cycloalkyl substituted by 1, 2 or 3C₁-C₁₀alkyl are 3-methylcyclohexyl and 2,3-dimethylcyclohexyl.

An example of cyclohexylmethyl substituted by 1, 2 or 3 C₁-C₁₀alkyl is1-cyclohexylethyl.

An example of C₅-C₉cycloalkenyl is cyclohexenyl.

An example of C₅-C₉cycloalkenyl substituted by 1, 2 or 3 C₁-C₁₀alkyl ismethylcyclohexenyl.

Examples of phenyl substituted by 1, 2 or 3 radicals selected from thegroup consisting of C₁-C₁₀alkyl, C₁-C₁₀alkyloxy, hydroxy, halogen,trihalogenmethyl, trihalogenmethoxy, benzoyl, phenylamino, acylamino andphenylazo are 4-methylphenyl, 2-ethylphenyl, 4-ethylphenyl,4-isopropylphenyl, 4-tert-butylphenyl, 4-sec-butylphenyl,4-isobutylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl,2,4-dimethylphenyl, 2,6-diethylphenyl, 2-ethyl-6-methylphenyl,2,6-diisopropylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-hydroxyphenyl,4-fluorophenyl, 3,5-difluorophenyl, 2-chlorophenyl, 3-chlorophenyl,3-chloro-6-methylphenyl, 3,5-di(trifluoromethyl)phenyl,4-trifluoromethoxyphenyl, 2-benzoylphenyl, 4-phenylaminophenyl,4-acetamidophenyl and 4-(phenylazo)phenyl.

A preferred example is 3,4-Dimethylphenyl.

Examples of C7-C₉phenylalkyl are benzyl and 2-phenylethyl. Benzyl ispreferred.

Examples of C₇-C₉phenylalkyl which is substituted on the phenyl by 1, 2or 3 radicals selected from the group consisting of C₁-C₁₀alkyl,C₁-C₁₀alkoxy and hydroxy are methylbenzyl, dimethylbenzyl,trimethylbenzyl, tert-butylbenzyl, methoxybenzyl and3,5-di-tert-butyl-4-hydroxybenzyl.

An example of naphthyl substituted by C₁-C₁₀alkyl is methylnaphthyl.

Examples of a 5 to 6 membered heterocyclic group are 2-picolyl,(2-furyl)methyl, (2-tetrahydrofuryl)methyl, 2-pyrimidyl,6-methyl-2-pyridyl, 1,2,4-triazol-3-yl and 2-(1-piperazinyl)ethyl.

The polypropylene resin of component (1) has preferably a content ofPβ-form crystals of 10 to 98%, in particular 15 to 80%.

Further examples of a suitable content of the β-form crystals are,depending on the desired application of the polypropylene resin, 10 to95%, 10 to 90%, 10 to 85%, 10 to 80%, 10 to 75%, 10to 70%, 10to 65%,10to 60%, 10to 55%, 10to 50%, 10to 45%, 10to 40%, 10to 35%, 10to 30%, 20to 95%, 20to 90%, 20 to 85%,.20 to 80%, 20to 75%, 20 to 70%, 20 to 65%,20 to 60%, 20 to 55%, 20 to 50%, 20 to 45%, 20 to 40%, 20 to 35%, 20 to30%, 30to 95%, 30to 90%, 30to 85%, 30to 80%, 30to 75%, 30to 70%, 30to65%, 30 to 60%, 30 to 55%, 30 to 50%, 30 to 45%, 30 to 40%, 35 to 95%,35 to 90%, 35 to 85%, 35 to 80%, 35 to 75%, 35 to 70%, 35 to 65%, 35 to60%, 35 to 55%, 35 to 50%, 35 to 45%, 40 to 95%, 40 to 90%, 40 to 85%,40 to 80%, 40 to 75%, 40 to 70%, 40 to 65%, 40 to 60%, 40 to 55%, 40 to50%, 45 to 95%, 45 to 90%, 45 to 85%, 45 to 80%, 45 to 75%, 45to 70%,45to 65%, 45to 60%, 45to 55, 50to 95%, 50to 90%, 50to 85%, 50to 80%,50to 75%, 50to 70%, 50to 65%, 50to 60%, 55to 90%, 55to 85%, 55to 80%,55to 75%, 55to 70%, 55to 65%, 60to 95%, 60to 90%, 60to 85%, 60to 80%,60to 75%, 60 to 70%, 65 to 95%, 65 to 90%, 65 to 85%, 65 to 80%, 70 to95%, 70 to 90%, 70 to 85% and 70to 80%.

According to a preferred embodiment of the present invention, thepolypropylene resin has a haze which is greater than 62%, in particulargreater than 70% or 80%; the haze value being measured at a plate,preferably prepared by injection molding, of 1.1 -1.2 mm thickness. Thehaze value in a range from 65 to 99%, in particular 70 to 99%, 75 to 99%or 80 to 99% is particularly preferred.

The haze is determined according to ASTM D 1003. Haze is defined as thatpercentage transmitted light which in passing through a specimen (plate)deviates from the incident beam by more than 2.5° on the average.Clarity is evaluated in the angle range smaller than 2.5°. The specimenshall have substantially plane-parallel surfaces free of dust, grease,scratches, and blemishes, and it shall be free of distinct internalvoids and particles.

According to a preferred embodiment of the present invention component(1) is a polypropylene homopolymer.

Polypropylene homopolymer also covers long chain branched polypropylene.

Polypropylene, can be prepared by different methods. Examples aredescribed in the following:

Catalytic polymerization using a catalyst that normally contains one ormore than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

According to a further preferred embodiment of the present invention,component (1) is a polypropylene random copolymer, alternating orsegmented copolymer or block copolymer containing one or more comonomersselected from the group consisting of ethylene, C₄-C₂₀-α-olefin,vinylcyclohexane, vinylcyclohexene, C₄-C₂₀alkandiene,C₅-C₁₂cycloalkandiene and norbornene derivatives; the total amount ofpropylene and the comonomer(s) being 100%.

Polypropylene copolymer also covers long chain branched polypropylenecopolymer.

Examples of suitable C₄-C₂₀α-olefins are 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and4-methyl-1-pentene.

Examples of suitable C₄-C₂₀alkandienes are hexadiene and octadiene.

Examples of suitable C₅-C₁₂cycloalkandienes are cyclopentadiene,cyclohexadiene and cyclooctadiene.

Examples of suitable norbornene derivatives are5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCP) andmethylene-domethylene-hexahydronaphthaline (MEN).

A propylene/ethylene copolymer contains for example 50 to 99.9%,preferably 80 to 99.9%, in particular 90 to 99.9%, by weight ofpropylene.

A propylene copolymer wherein the comonomer is a C₉-C₂₀α-olefin such ase.g. 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene or 1-eicosene; C₉-C₂₀alkandiene,C₉-C₁₂cycloalkandiene or a norbornene derivative such as e.g.5-ethylidene-2-norbornene (ENB) ormethylene-domethylene-hexahydronaphthaline (MEN) contains preferablymore than 90mol %, in particular 90 to 99.9mol % or 90 to 99mol %, ofpropylene.

A propylene copolymer wherein the comonomer is a C₄-C₈α-olefin such ase.g. 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene or4-methyl-1-pentene; vinylcyclohexane, vinylcyclohexene, C₄-C₈alkandieneor C₅-C₈cycloalkandiene contains preferably more than 80mol %, inparticular 80 to 99.9mol % or 80 to 99mol %, of propylene.

Further examples of component (1) are propylene/isobutylene copolymer,propylene/butadiene copolymer, propylene/cycloolefin copolymer,terpolymers of propylene with ethylene and a diene such as hexadiene,dicyclopentadiene or ethylidene-norbornene; propylene/1-olefincopolymers where the 1-olefin is generated in situ; and propylene/carbonmonoxide copolymers.

According to another preferred embodiment of the present inventioncomponent (1) is a thermoplastic polyolefin (TPO).

Thermoplastic polyolefin (TPO) means in particular elastomers thatexhibit rubber characteristics and are based on polyolefins. These arepreferably copolymers from ethylene and propylene (EPM) or terpolymerscomprising ethylene, propylene and a non-conjugated diene (EPDM) and thelike.

The present invention also relates to a composition which additionallycontains

-   (3) a further polymer, in particular a synthetic polymer, preferably    EPDM or EPM; with the proviso that component (3) is different from    component (1).

Examples of suitable polymers are

-   1. Polymers of monoolefins and diolefins, for example    polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,    polyvinylcyclohexane, polyisoprene or polybutadiene, as well as    polymers of cycloolefins, for instance of cyclopentene or    norbornene, polyethylene (which optionally can be crosslinked), for    example high density polyethylene (HDPE), high density and high    molecular weight polyethylene (HDPE-HMW), high density and ultrahigh    molecular weight polyethylene (HDPE-UHMW), medium density    polyethylene (MDPE), low density polyethylene (LDPE), linear low    density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).

-   2. Mixtures of the polymers mentioned under 1), for example mixtures    of polypropylene with polyisobutylene, polypropylene with    polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of    different types of polyethylene (for example LDPE/HDPE).

-   3. Copolymers of monoolefins and diolefins with each other or with    other vinyl monomers, for example ethylene/propylene copolymers,    linear low density polyethylene (LLDPE) and mixtures thereof with    low density polyethylene (LDPE), propylene/but-1-ene copolymers,    propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,    ethylene/hexene copolymers, ethylene/methylpentene copolymers,    ethylene/heptene copolymers, ethylene/octene copolymers,    ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin    copolymers (e.g. ethylene/norbornene like COC), ethylene/1-olefins    copolymers, where the 1-olefin is generated in-situ;    propylene/butadiene copolymers, isobutylene/isoprene copolymers,    ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate    copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl    acetate copolymers or ethylene/acrylic acid copolymers and their    salts (ionomers) as well as terpolymers of ethylene with propylene    and a diene such as hexadiene, dicyclopentadiene or    ethylidene-norbornene; and mixtures of such copolymers with one    another and with polymers mentioned in 1) above, for example    polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl    acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers    (EM), LLDPE/EVA, LLDPE/EAA and alternating or random    polyalkylene/carbon monoxide copolymers and mixtures thereof with    other polymers, for example polyamides.

-   4. Hydrocarbon resins (for example C₅-C₉) including hydrogenated    modifications thereof (e.g. tackifiers) and mixtures of    polyalkylenes and starch.

Homopolymers and copolymers from 1.)-4.) may have any stereostructureincluding syndiotactic, isotactic, hemi-isotactic or atactic; whereatactic polymers are preferred. Stereoblock polymers are also included.

-   5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).-   6. Aromatic homopolymers and copolymers derived from vinyl aromatic    monomers including styrene, α-methylstyrene, all isomers of vinyl    toluene, especially p-vinyltoluene, all isomers of ethyl styrene,    propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl    anthracene, and mixtures thereof. Homopolymers and copolymers may    have any stereostructure including syndiotactic, isotactic,    hemi-isotactic or atactic; where atactic polymers are preferred.    Stereoblock polymers are also included.-   6a. Copolymers including aforementioned vinyl aromatic monomers and    comonomers selected from ethylene, propylene, dienes, nitriles,    acids, maleic anhydrides, maleimides, vinyl acetate and vinyl    chloride or acrylic derivatives and mixtures thereof, for example    styrene/butadiene, styrene/acrylonitrile, styrene/ethylene    (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl    acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic    anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high    impact strength of styrene copolymers and another polymer, for    example a polyacrylate, a diene polymer or an    ethylene/propylene/diene terpolymer; and block copolymers of styrene    such as styrene/butadiene/styrene, styrene/isoprene/styrene,    styrene/ethylene/butylene/styrene or    styrene/ethylene/propylene/styrene.-   6b. Hydrogenated aromatic polymers derived from hydrogenation of    polymers mentioned under 6.), especially including    polycyclohexylethylene (PCHE) prepared by hydrogenating atactic    polystyrene, often referred to as polyvinylcyclohexane (PVCH).-   6c. Hydrogenated aromatic polymers derived from hydrogenation of    polymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure includingsyndiotactic, isotactic, hemi-isotactic or atactic; where atacticpolymers are preferred. Stereoblock polymers are also included.

-   7. Graft copolymers of vinyl aromatic monomers such as styrene or    α-methylstyrene, for example styrene on polybutadiene, styrene on    polybutadiene-styrene or polybutadiene-acrylonitrile copolymers;    styrene and acrylonitrile (or methacrylonitrile) on polybutadiene;    styrene, acrylonitrile and methyl methacrylate on polybutadiene;    styrene and maleic anhydride on polybutadiene; styrene,    acrylonitrile and maleic anhydride or maleimide on polybutadiene;    styrene and maleimide on polybutadiene; styrene and alkyl acrylates    or methacrylates on polybutadiene; styrene and acrylonitrile on    ethylene/propylene/diene terpolymers; styrene and acrylonitrile on    polyalkyl acrylates or polyalkyl methacrylates, styrene and    acrylonitrile on acrylate/butadiene copolymers, as well as mixtures    thereof with the copolymers listed under 6), for example the    copolymer mixtures known as ABS, MBS, ASA or AES polymers.-   8. Halogen-containing polymers such as polychloroprene, chlorinated    rubbers, chlorinated and brominated copolymer of    isobutylene-isoprene (halobutyl rubber), chlorinated or    sulfochlorinated polyethylene, copolymers of ethylene and    chlorinated ethylene, epichlorohydrin homo- and copolymers,    especially polymers of halogen-containing vinyl compounds, for    example polyvinyl chloride, polyvinylidene chloride, polyvinyl    fluoride, polyvinylidene fluoride, as well as copolymers thereof    such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl    acetate or vinylidene chloride/vinyl acetate copolymers.-   9. Polymers derived from α,β-unsaturated acids and derivatives    thereof such as polyacrylates and polymethacrylates; polymethyl    methacrylates, polyacrylamides and polyacrylonitriles,    impact-modified with butyl acrylate.-   10. Copolymers of the monomers mentioned under 9) with each other or    with other unsaturated monomers, for example acrylonitrile/butadiene    copolymers, acrylonitrile/alkyl acrylate copolymers,    acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide    copolymers or acrylonitrile/alkyl methacrylate/butadiene    terpolymers.-   11. Polymers derived from unsaturated alcohols and amines or the    acyl derivatives or acetals thereof, for example polyvinyl alcohol,    polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl    maleate, polyvinyl butyral, polyallyl phthalate or polyallyl    melamine; as well as their copolymers with olefins mentioned in 1)    above.-   12. Homopolymers and copolymers of cyclic ethers such as    polyalkylene glycols, polyethylene oxide, polypropylene oxide or    copolymers thereof with bisglycidyl ethers.-   13. Polyacetals such as polyoxymethylene and those polyoxymethylenes    which contain ethylene oxide as a comonomer; polyacetals modified    with thermoplastic polyurethanes, acrylates or MBS.-   14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene    oxides with styrene polymers or polyamides.-   15. Polyurethanes derived from hydroxyl-terminated polyethers,    polyesters or polybutadienes on the one hand and aliphatic or    aromatic polyisocyanates on the other, as well as precursors    thereof.-   16. Polyamides and copolyamides derived from diamines and    dicarboxylic acids and/or from aminocarboxylic acids or the    corresponding lactams, for example polyamide 4, polyamide 6,    aminocarboxylic acids or the corresponding lactams, for example    polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6,    12/12, polyamide 11, polyamide 12, aromatic polyamides    hexamethylenediamine and isophthalic or/and terephthalic acid and    with or without an elastomer as modifier, for example    poly-2,4,4,-trimethylhexamethylene terephthalamide or    poly-m-phenylene isophthalamide; and also block copolymers of the    aforementioned polyamides with polyolefins, olefin copolymers,    ionomers or chemically bonded or grafted elastomers; or with    polyethers, e.g. with polyethylene glycol, polypropylene glycol or    polytetramethylene glycol; as well as polyamides or copolyamides    modified with EPDM or ABS; and polyamides condensed during    processing (RIM polyamide systems).-   17. Polyureas, polyimides, polyamide-imides, polyetherimids,    polyesterimids, polyhydantoins and polybenzimidazoles.-   18. Polyesters derived from dicarboxylic acids and diols and/or from    hydroxycarboxylic acids or the corresponding lactones, for example    polyethylene terephthalate, polybutylene terephthalate,    poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene    naphthalate (PAN) and polyhydroxybenzoates, as well as block    copolyether esters derived from hydroxyl-terminated polyethers; and    also polyesters modified with polycarbonates or MBS.-   19. Polycarbonates and polyester carbonates.-   20. Polyketones.-   21. Polysulfones, polyether sulfones and polyether ketones.-   22. Crosslinked polymers derived from aldehydes on the one hand and    phenols, ureas and melamines on the other hand, such as    phenol/formaldehyde resins, urea/formaldehyde resins and    melamine/formaldehyde resins.-   23. Drying and non-drying alkyd resins.-   24. Unsaturated polyester resins derived from copolyesters of    saturated and unsaturated dicarboxylic acids with polyhydric    alcohols and vinyl compounds as crosslinking agents, and also    halogen-containing modifications thereof of low flammability.-   25. Crosslinkable acrylic resins derived from substituted acrylates,    for example epoxy acrylates, urethane acrylates or polyester    acrylates.-   26. Alkyd resins, polyester resins and acrylate resins crosslinked    with melamine resins, urea resins, isocyanates, isocyanurates,    polyisocyanates or epoxy resins.-   27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,    heterocyclic or aromatic glycidyl compounds, e.g. products of    diglycidyl ethers of bisphenol A and bisphenol F, which are    crosslinked with customary hardeners such as anhydrides or amines,    with or without accelerators.-   28. Natural polymers such as cellulose, rubber, gelatin and    chemically modified homologous derivatives thereof, for example    cellulose acetates, cellulose propionates and cellulose butyrates,    or the cellulose ethers such as methyl cellulose; as well as rosins    and their derivatives.-   29. Blends of the aforementioned polymers (polyblends), for example    PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,    PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic    PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA    6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or    PBT/PET/PC.-   30. Aqueous emulsions of natural or synthetic rubber, e.g. natural    latex or latices of carboxylated styrene/butadiene copolymers.

Preferred examples of a blend of components (1) and (3) are blends ofpolypropylene with propylene/ethylene copolymers, propylene/butylenecopolymers, polyethylene, e.g. HDPE or LDPE; polybutene,polyisobutylene, poly-4-methylpentene or alternating or randompolyalkylene/carbon monoxide copolymers.

According to a preferred embodiment of the present invention,

-   R₁, R₂ and R₃, independently of one another, are-   C₁-C₂₀alkyl,-   C₂-C₁₀alkyl substituted by C₁-C₄alkylamino, di(C₁-C₄alkyl)amino,    C₁-C₄alkyloxy or hydroxy;-   C₃-C₂₀alkenyl,-   C₅-C₁₂cycloalkyl,-   C₅-C₁₂cycloalkyl substituted by 1, 2 or 3 C₁-C₄alkyl;-   cyclohexylmethyl;-   cyclohexylmethyl substituted by 1, 2 or 3 C₁-C₄alkyl;-   phenyl substituted by 1, 2 or 3 radicals selected from the group    consisting of C₁-C₄alkyl,-   C₁-C₄alkyloxy or hydroxy;-   benzyl,-   benzyl which is substituted on the phenyl by 1, 2 or 3 radicals    selected from the group consisting of C₁-C₄alkyl, C₁-C₄alkoxy and    hydroxy;-   naphthyl, or-   naphthyl substituted by C₁-C₄alkyl.

According to a further preferred embodiment of the present invention

-   R₁, R₂ and R₃, independently of one another, are-   C₁-C₂₀alkyl,-   C₂-C₆alkyl substituted by C₁-C₄alkylamino, di(C₁-C₄alkyl)amino or    C₁-C₄alkyloxy;-   C₅-C₁₂cycloalkyl,-   C₅-C₁₂cycloalkyl substituted by 1, 2 or 3 C₁-C₄alkyl;-   cyclohexylmethyl;-   cyclohexylmethyl substituted by 1, 2 or 3 C₁-C₄alkyl;-   phenyl substituted by 1, 2 or 3 C₁-C₄alkyl;-   benzyl,-   benzyl which is substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl;    or-   naphthyl.

According to a particularly preferred embodiment of the presentinvention

-   R₁, R₂ and R₃, independently of one another, are-   butyl, octyl or octadecyl,-   3-dimethylaminopropyl, 3-methoxypropyl or 2-methoxyethyl,-   cyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl,-   3-methylcyclohexyl or 2,3-dimethylcyclohexyl,-   1-cyclohexylethyl,-   3,4-dimethylphenyl,-   benzyl, or-   naphthyl.

R₁, R₂ and R₃ are preferably identical and are preferably2,3-dimethylcyclohexyl, tert-octyl or cyclooctyl.

The amount of the β-nucleating agent (component (2)) to be added to thepolypropylene resin is not critical insofar as the desired effect can beobtained. Generally, it is used in an amount effective for increasingthe content of the β-crystal form. 0.0001 to 5%, in particular 0.001 to2%, 0.05 to 1%, 0.1 to 1% or 0.15 to 1%, relative to the weight ofcomponent (1), are suitable.

Thus, the β-nucleating agent of the invention is capable of causing acrystalline polypropylene resin to undergo transition to the β-crystalform at a very low level of addition and a molded product having aβ-form crystal content as indicated above can be obtained under suitablemolding conditions.

Component (3) is preferably present in the composition according to thepresent invention in an amount of 1 to 90%, for example 2 to 80% or 5 to50%, relative to the weight of component (1).

A further embodiment of the present invention is a method for providinga polypropylene resin with a content of β-form crystals of at least 10%calculated by means of the following equationβ-form crystal content (%)=100×P _(β1)/(P _(α1) +P _(α2) +P _(α3) +P_(β1))

where P_(α1) to P_(α3) are respective peak heights (maxima) of theβ-form and P_(β1) is a peak height (maximum) of the β-form determined bywide angle X-ray scattering, which comprises incorporating into thepolypropylene resin one or more β-nucleating agents of the formula (I).

Another embodiment of the present invention is the use of a compound ofthe formula (I) as β-nucleating agent for a polypropylene resin.

The resin compositions of the present invention may be prepared bystandard procedures, well known to those skilled in the art, ofcompounding, such as mixing the prescribed components in a conventionalmixer by e.g. dry-blending or solution spraying and melting and kneadingthe mixture with a single- or twin-screw extruder, or the like.

The β-nucleating agent of the formula (I) can be added to thepolypropylene resin at an optional stage, i.e. either during thepolymerization reaction or after the polymer has been prepared.

To the resin compositions of the present invention, additional materialscan be added in a concentration range that does not adversely affect thebeneficial effects of the invention. These materials may includestabilizers, antioxidants, antibacterial agents, ultraviolet absorbers,thermostabilizers, light stabilizers, neutralizers, antistatic agents,antiblocking agents, heavy metal inactivation agents, flame retardants,lubricants, peroxides, hydrotalcite, foaming agents, elastomers,processing aids, additional nucleating agents, reinforcing matter,plasticizer and the like and mixtures thereof.

More detailed examples of these conventional additives are listed below.

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethyl-phenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctyl-thiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocorsherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butyl-phenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5di-tert-butyl-4-hydroxy-benzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylol-propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)protionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3.5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1, supplied by Uniroyal).

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyidiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyl-diphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octylphenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilisers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonyl-ethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂

₂, where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, for example4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyidithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); a condensate of 1,6-hexanediamine and2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,a diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, areaction product of maleic acid anhydride-α-olefin copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenol]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosohites and phosphonites, for example triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-di-cumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

The following phosphites are especially preferred:

Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos®168, Ciba-Geigy),tris(nonylphenyl)phosphite,

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-alpha-phenylnitrone,N-ethyl-alpha-methyinitrone, N-octyl-alpha-heptylnitrone,N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone,N-hexadecyl-alpha-pentadecyinitrone,N-octadecyl-alpha-heptadecyinitrone,N-hexadecyl-alpha-heptadecyinitrone,N-ocatadecyl-alpha-pentadecyinitrone,N-heptadecyl-alpha-heptadecylnitrone,N-octadecyl-alpha-hexadecylnitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyidithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

11. Conventional nucleating agents, for example inorganic substances,such as talcum, metal oxides, such as titanium dioxide or magnesiumoxide, phosphates, carbonates or sulfates of, preferably, alkaline earthmetals; organic compounds, such as mono- or polycarboxylic acids and thesalts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid,diphenylacetic acid, sodium succinate or sodium benzoate; polymericcompounds, such as ionic copolymers (ionomers). Especially preferred are1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene)sorbitol, and1,3:2,4-di(benzylidene)sorbitol.

12. Other additives, for example plasticisers, lubricants, rheologyadditives, catalysts, flow-control agents, optical brighteners,flameproofing agents, antistatic agents and blowing agents.

13. Benzofuranones and Indolinones, for example those disclosed in U.S.Pat. Nos. 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643;DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-(2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzo-furan-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.

The weight ratio of the β-nucleating agent(s) (component (2)) to theconventional additive is for example 1:1000 to 100:1, preferably 1:100to 100:1, 1:90 to 90:1, 1:80 to 80:1, 1:70 to 70:1, 1:60 to 60:1, 1:50to 50:1, 1:40 to 40:1, 1:30 to 30:1, 1:20 to 20:1, 1:10 to 10:1, 1:5 to5:1, 1:4 to 4:1, 1:3 to 3:1, 1:2 to 2:1 or 1:1. In general, theconventional additive is present in the composition of this invention inan amount of preferably 0.0001 to 5% or 0.001 to 3%, in particular 0.01to 2% or 0.01 to 0.25%, relative to the weight of component (1).

The polypropylene resin of component (I) preferably contains one or moreprocess stabilizers, e.g. in an amount of 0.001 to 2%, relative to theweight of component (1).

Examples of processing of the resin compositions according to thepresent invention are: Injection blow molding, extrusion, blow molding,rotomolding, in mold decoration (back injection), slush molding,injection molding, co-injection molding, forming, compression molding,pressing, film extrusion (cast film; blown film), fiber spinning (woven,non-woven), drawing (uniaxial, biaxial), annealing, deep drawing,calandering, mechanical transformation, sintering, coextrusion, coating,lamination, crosslinking (radiation, peroxide, silane), vapordeposition, weld together, glue, vulkanization, thermoforming, pipeextrusion, profile extrusion, sheet extrusion; sheet casting, spincoating, strapping, foaming, recycling/rework, extrusion coating,visbreaking (peroxide, thermal), fiber melt blown, spun bonded, surfacetreatment (corona discharge, flame, plasma), sterilization (by gammarays, electron beams), gel-coating, tape extrusion, SMC-process orplastisol.

The resulting crystalline polypropylene resin composition of the presentinvention are preferably molded by injection, compression, blow molding,roto molding and/or other known molding techniques utilizing theconventional molding machines. Molding conditions may be those commonlyemployed. Typical preferred molding conditions may be as follows.Injection molding: resin temperature about 180 to 320° C., preferablyabout 200 to 300° C.; mold temperature about 0 to 120° C., preferablyabout 30 to 80° C. Blow molding: resin temperature about 180 to 300° C.,preferably about 200 to 280° C.; mold temperature about 20 to 140° C.,preferably about 60 to 120° C. Compression molding: temperature ofmelted resin about 180 to 300° C., preferably about 200 to 280° C.;cooling temperature about 10 to 125° C., preferably about 30 to 100° C.

Molded products, which contain much higher proportion of β-crystal formthan the reference material and which are satisfactory in the aspect ofcolor, can be easily obtained by molding under the above-mentionedmolding condition the resin composition of the invention prepared withuse of, for instance, the above-mentioned mixing method. Compared withthe conventional polypropylene pellet which normally does notsubstantially contain β-crystals but is predominantly composed ofα-crystals, the polypropylene molded product has a lower melting pointand requires a lower force for deformation under heating. Therefore, themolded products contribute a great deal to improved secondaryprocessability and mechanical characteristics. The products encompass awide variety of forms such as packaging, containers, bumpers, housing,technical article (e.g. gear) and so on.

With the resin compositions of the present invention, the ratio of α- toβ-form in the final product can be controlled as desired by suitablesolidification conditions. It is possible to control the ratio of α- toβ-form by appropriately selecting cooling conditions under the abovemolding condition. This characteristic is beneficial particularly in thesurface roughening of, for instance, biaxially oriented films andfibres. The film having such a roughened surface displays excellentantiblocking property, printability and adhesion, etc. and is of greatuse in the fields of packaging film, printing paper, tracing paper,oil-immersion type plastic capacitors and so on.

The resin compositions according to the present invention can beadvantageously used for the preparation of various shaped articles.Examples are:

-   I-1) Floating devices, marine applications, pontoons, buoys, plastic    lumber for decks, piers, boats, kayaks, oars, and beach    reinforcements.-   I-2) Automotive applications, in particular bumpers, dashboards,    battery, rear and front linings, moldings parts under the hood, hat    shelf, trunk linings, interior linings, air bag covers, electronic    moldings for fittings (lights), panes for dashboards, headlamp    glass, instrument panel, exterior linings, upholstery, automotive    lights, head lights, parking lights, rear lights, stop lights,    interior and exterior trims; door panels; gas tank; glazing front    side; rear windows; seat backing, exterior panels, wire insulation,    profile extrusion for sealing, cladding, pillar covers, chassis    parts, exhaust systems, fuel filter/filler, fuel pumps, fuel tank,    body side mouldings, convertible tops, exterior mirrors, exterior    trim, fasteners/fixings, front end module, glass, hinges, lock    systems, luggage/roof racks, pressed/stamped parts, seals, side    impact protection, sound deadener/insulator and sunroof.-   I-3) Road traffic devices, in particular sign postings, posts for    road marking, car accessories, warning triangles, medical cases,    helmets, tires.-   I-4) Devices for plane, railway, motor car (car, motorbike)    including furnishings.-   I-5) Devices for space applications, in particular rockets and    satellites, e.g. reentry shields.-   I-6) Devices for architecture and design, mining applications,    acoustic quietized systems, street refuges, and shelters.-   II-1) Appliances, cases and coverings in general and    electric/electronic devices (personal computer, telephone, portable    phone, printer, television-sets, audio and video devices), flower    pots, satellite TV bowl, and panel devices.-   II-2) Jacketing for other materials such as steel or textiles.-   II-3) Devices for the electronic industry, in particular insulation    for plugs, especially computer plugs, cases for electric and    electronic parts, printed boards, and materials for electronic data    storage such as chips, check cards or credit cards.-   II-4) Electric appliances, in particular washing machines, tumblers,    ovens (microwave oven), dish-washers, mixers, and irons.-   II-5) Covers for lights (e.g. street-lights, lamp-shades).-   II-6) Applications in wire and cable (semi-conductor, insulation and    cable-jacketing).-   II-7) Foils for condensers, refrigerators, heating devices, air    conditioners, encapsulating of electronics, semi-conductors, coffee    machines, and vacuum cleaners.-   III-1) Technical articles such as cogwheel (gear), slide fittings,    spacers, screws, bolts, handles, and knobs.-   III-2) Rotor blades, ventilators and windmill vanes, solar devices,    swimming pools, swimming pool covers, pool liners, pond liners,    closets, wardrobes, dividing walls, slat walls, folding walls,    roofs, shutters (e.g. roller shutters), fittings, connections    between pipes, sleeves, and conveyor belts.-   III-3) Sanitary articles, in particular shower cubicles, lavatory    seats, covers, and sinks.-   III-4) Hygienic articles, in particular diapers (babies, adult    incontinence), feminine hygiene articles, shower curtains, brushes,    mats, tubs, mobile toilets, tooth brushes, and bed pans.-   III-5) Pipes (cross-linked or not) for water, waste water and    chemicals, pipes for wire and cable protection, pipes for gas, oil    and sewage, guttering, down pipes, and drainage systems.-   III-6) Profiles of any geometry (window panes) and siding.-   III-7) Glass substitutes, in particular extruded plates, glazing for    buildings (monolithic, twin or multiwall), aircraft, schools,    extruded sheets, window film for architectural glazing, train,    transportation, sanitary articles, and greenhouse.-   III-8) Plates (walls, cutting board), extrusion-coating    (photographic paper, tetrapack and pipe coating), silos, wood    substitute, plastic lumber, wood composites, walls, surfaces,    furniture, decorative foil, floor coverings (interior and exterior    applications), flooring, duck boards, and tiles.-   III-9) Intake and outlet manifolds.-   III-10) Cement-, concrete-, composite-applications and covers,    siding and cladding, hand rails, banisters, kitchen work tops,    roofing, roofing sheets, tiles, and tarpaulins.-   IV-1) Plates (walls and cutting board), trays, artificial grass,    astroturf, artificial covering for stadium rings (athletics),    artificial floor for stadium rings (athletics), and tapes.-   IV-2) Woven fabrics continuous and staple, fibers (carpets/hygienic    articles/geotextiles/monofilaments; filters; wipes/curtains    (shades)/medical applications), bulk fibers (applications such as    gown/protection clothes), nets, ropes, cables, strings, cords,    threads, safety seat-belts, clothes, underwear, gloves; boots;    rubber boots, intimate apparel, garments, swimwear, sportswear,    umbrellas (parasol, sunshade), parachutes, paraglides, sails,    “balloon-silk”, camping articles, tents, airbeds, sun beds, bulk    bags, and bags.-   IV-3) Membranes, insulation, covers and seals for roofs, tunnels,    dumps, ponds, dumps, walls roofing membranes, geomembranes, swimming    pools, curtains (shades)/sun-shields, awnings, canopies, wallpaper,    food packing and wrapping (flexible and solid), medical packaging    (flexible & solid), airbags/safety belts, arm- and head rests,    carpets, centre console, dashboard, cockpits, door, overhead console    module, door trim, headliners, interior lighting, interior mirrors,    parcel shelf, rear luggage cover, seats, steering column, steering    wheel, textiles, and trunk trim.-   V) Films (packaging, dump, laminating, agriculture and horticulture,    greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, waste    bags, wallpaper, stretch film, raffia, desalination film, batteries,    and connectors.-   VI-1) Food packing and wrapping (flexible and solid), BOPP, BOPET,    bottles.-   VI-2) Storage systems such as boxes (crates), luggage, chest,    household boxes, pallets, shelves, tracks, screw boxes, packs, and    cans.-   VI-3) Cartridges, syringes, medical applications, containers for any    transportation, waste baskets and waste bins, waste bags, bins, dust    bins, bin liners, wheely bins, container in general, tanks for    water/used water/chemistry/gas/oil/gasoline/diesel; tank liners,    boxes, crates, battery cases, troughs, medical devices such as    piston, ophthalmic applications, diagnostic devices, and packing for    pharmaceuticals blister.-   VII-1) Extrusion coating (photo paper, tetrapack, pipe coating),    household articles of any kind (e.g. appliances, thermos    bottle/clothes hanger), fastening systems such as plugs, wire and    cable clamps, zippers, closures, locks, and snap-closures.-   VII-2) Support devices, articles for the leisure time such as sports    and fitness devices, gymnastics mats, ski-boots, inline-skates,    skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops,    tops and stoppers for bottles, and cans.-   VII-3) Furniture in general, foamed articles (cushions, impact    absorbers), foams, sponges, dish clothes, mats, garden chairs,    stadium seats, tables, couches, toys, building kits    (boards/figures/balls), playhouses, slides, and play vehicles.-   VII-4) Materials for optical and magnetic data storage.-   VII-5) Kitchen ware (eating, drinking, cooking, storing).-   VII-6) Boxes for CD's, cassettes and video tapes; DVD electronic    articles, office supplies of any kind (ball-point pens, stamps and    ink-pads, mouse, shelves, tracks), bottles of any volume and content    (drinks, detergents, cosmetics including perfumes), and adhesive    tapes.-   VII-7) Footwear (shoes/shoe-soles), insoles, spats, adhesives,    structural adhesives, food boxes (fruit, vegetables, meat, fish),    synthetic paper, labels for bottles, couches, artificial joints    (human), printing plates (flexographic), printed circuit boards, and    display technologies.-   VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin),    wollastonite, pigments, carbon black, TiO₂, mica, nanocomposites,    dolomite, silicates, glass, asbestos).

Thus, a further embodiment of the present invention relates to a shapedarticle, in particular a film fiber, profile, pipe, bottle, tank orcontainer, containing a resin composition as described above.

A molded article is preferred. The molding is in particular effected byinjection, blow, compression, roto-molding or slush-molding orextrusion.

A further embodiment of the present invention relates to amonoaxially-oriented film or a biaxially-oriented film which has beenformed by stretching a film containing a composition as described above.

Another embodiment of the present invention is a fiber which has beenformed by stretching a fiber containing a composition as describedabove.

The present invention further relates to a multilayer system in whichone or more layers contain a composition as described above.

The compounds of the formula (I) can be prepared in analogy to knownprocesses, for example by reacting an appropriate amine with1,3,5-benzenetricarboxylic acid trichloride as described for example inthe standard works such as Houben-Weyl, Methoden der Organischen Chemie[Methods of Organic Chemistry], published by Georg Thieme, Stuttgart),under reaction conditions which are known. In carrying out thesereactions, it is also possible to take advantage of variants known perse which are not specifically mentioned here. The starting substancescan, if so desired also be formed in situ, by not isolating them out ofthe reaction mixture but immediately reacting them further to thecompounds of the formula (I). Working Examples A to C describe arepresentative method of the preparation.

Examples of appropriate amines are:

-   isopropylamine,-   n-butylamine,-   sec-butylamine-   tert-butylamine,-   n-pentylamine,-   1,1 -dimethylpropylamine,-   1,2-dimethylpropylamine,-   3-methylbutylamine,-   n-hexylamine,-   n-heptylamine,-   n-octylamine,-   2-ethylhexylamine,-   tert-octylamine (1,1,3,3-tetramethylbutylamine),-   isononylamine,-   n-dodecylamine,-   tridecylamine,-   tallowamine,-   2-dimethylaminoethylamine,-   2-diethylaminoethylamine,-   3-dimethylaminopropylamine,-   3-diethylaminopropylamine,-   3-methylaminopropylamine,-   2-methoxyethylamine,-   2-ethoxyethylamine,-   2-methoxypropylamine,-   2-ethoxypropylamine,-   3-isopropoxypropylamine,-   allylamine,-   oleylamine,-   cyclopentylamine,-   cyclohexylamine,-   2-methylcyclohexylamine,-   cyclohexylmethylamine,-   4-methylphenylamine (=4-methylaniline),-   2-ethylphenylamine (=2-ethylaniline),-   4-ethylphenylamine (=4-ethylaniline),-   4-isopropylphenylamine (=4-isopropylaniline),-   4-tert-butylphenylamine (=4-tert-butylaniline),-   4-sec-butylphenylamine (=4-sec-butylaniline),-   4-isobutylphenylamine (=4-isobutylaniline),-   3,5-dimethylphenylamine (=3,5-dimethylaniline),-   3,4-dimethylphenylamine (=3,4-dimethylaniline),-   2,4-dimethylphenylamine (=2,4-dimethylaniline),-   2,6-diethylphenylamine (=2,6-diethylaniline),-   2-ethyl-6-methylphenylamine (=2-ethyl-6-methylaniline),-   2,6-diisopropylphenylamine (=2,6-diisopropylaniline),-   4-methoxyphenylamine (=4-methoxyaniline),-   4-ethoxyphenylamine (=4-ethoxyaniline),-   4-hydroxyphenylamine (=4-hydroxyaniline),-   4-acetamidophenylamine (=4-acetamidoaniline),-   3-chlorophenylamine (=3-chloroaniline),-   2-chlorophenylamine (=2-chloroaniline),-   3-chloro-6-methylphenylamine,-   2-benzoylphenylamine (=2-benzoylaniline),-   4-phenylaminophenylamine,-   4-(phenylazo)phenylamine (=4-aminoazobenzene),-   benzylamine,-   2-phenylethylamine,-   1 -naphthylamine,-   adamantylamine,-   2-picolylamine,-   (2-furyl)methylamine,-   (2-tetrahydrofuryl)methylamine,-   2-pyrimidylamine,-   6-methyl-2-pyridylamine,-   1,2,4-triazol-3-ylamine, and-   2-(1-piperazinyl)ethylamine.

The following examples describe the present invention in greater detail.

Unless indicated otherwise, heretofore and hereinafter, all parts andpercentages are by weight and all temperatures are given in degreesCelsius (° C.). “Customary working up” means: addition to water,filtration of precipitate, extracting with organic solvent and/orpurifying the product by crystallization and/or chromatography and/orsublimation.

EXAMPLE A Preparation of the Compound of the Formula

4.20 g (33 mmol) of 2,3-dimethylcyclohexylamine (isomeric mixture) and0.1 g of dry LiCl are added under inert atmosphere to 70 ml of dryN-methylpyrrolidinone (NMP) and 15 ml of dry pyridine and cooled to 5°C. Then, 2.39 g (9 mmol) of 1,3,5-benzenetricarboxylic acid trichlorideare added. The reaction mixture is heated to 75° C. and stirred. After 2hours the reaction mixture is added to 300 ml of ice water. Theprecipitate was filtered off. Customary work-up (recrystallization fromN,N-dimethylformamide) gives 1,3,5-benzenetricarboxylic acidtris(2,3-dimethylcyclohexylamide).

Yield: 3.28 g (6.10 mmol)=67.8% of theory.

Melting point: 418° C. (under simultaneous evaporation).

¹H-NMR (CF₃COOD/CDCl₃ 1:1): δ=0.50-2.35 (m, 42H); 3.58-4.55 (m, 3H);8.50-8.88 (m, 3H).

¹³C-NMR (CF₃COOD/CDCl₃ 1:1): δ=5.0-58.0 (aliphatic carbon atoms) 130.8;134.3; 168.5.

IR (KBr, cm⁻¹): 3232; 3065; 2928; 1637; 1550; 1290.

MS (70 eV), m/z: 537 (M⁺, 5%).

EXAMPLE B Preparation of the Compound of the Formula

4.20 g (33 mmol) of cyclooctylamine and 0.1 g of dry LiCl are addedunder inert atmosphere to 70 ml of dry NMP and 15 ml of dry pyridine andcooled to 5° C. Then, 2.39 g (9 mmol) of 1,3,5-benzenetricarboxylic acidtrichloride are added. The reaction mixture is heated to 75° C. andstirred. After 2 hours the reaction mixture is added to 300 ml of icewater. Customary work-up (recrystallization from N,N-dimethylformamide)gives 1,3,5-benzenetricarboxylic acid tris(cyclooctylamide).

Yield: 4.02 g (7.48 mmol)=83.1% of theory.

Melting point: 402° C. (under simultaneous evaporation).

¹H-NMR (CF₃COOD/CDCl₁ 1:1): δ=1.46-2.07 (m, 42H); 4.15-4.36 (m, 3H);8.66 (s, 3H).

¹³C-NMR (CF₃COOD/CDCl₃ 1:1): δ=23.7; 25.5; 27.0; 31.9; 53.2; 130.9;134.3; 167.9.

IR (KBr, cm⁻¹): 3222; 3059; 2922; 1634; 1556; 1285.

MS (70 eV). m/z: 537 (M⁺, 42%).

EXAMPLE C Preparation of the Compound of the Formula

4.26 g (33 mmol) of 1,1,3,3-tetramethylbutylamine (tert-octylamine) and0.1 g of dry LiCl are added under inert atmosphere to 70 ml of dry NMPand 15 ml of dry pyridine and cooled to 5° C. Then, 2.39 g (9 mmol) of1,3,5-benzenetricarboxylic acid trichloride are added. The reactionmixture is heated to 75° C. and stirred. After 2 hours the reactionmixture is added to 300 ml of ice water. The precipitate is filteredoff. Customary work-up (recrystallization from methanol) gives1,3,5-benzenetricarboxylic acid tris(1,1,3,3-tetramethylbutylamide).

Yield: 3.40 g (6.25 mmol)=69.5% of theory.

Melting point: 315° C. (under simultaneous evaporation).

¹H-NMR (CF₃COOD/CDCl₃ 1:1): δ=1.03 (s, 27H); 1.58 (s, 18H); 1.95 (s,6H); 8.49 (s, 3H).

¹³C-NMR (CF₃COOD/CDCl₃ 1:1): δ=28.8; 31.0; 31.8; 51.1; 58.8; 130.3;135.4; 168.6.

IR (KBr, cm⁻¹): 3237; 3063; 2955; 1637; 1557; 1228.

MS (70 eV), m/z: 543 (M⁺, 46%).

The following compounds A-1 to A-5, A-7 and A-8 which are characterizedby their melting points (m.p.) are analogously prepared. The meltingpoint is determined in a DSC-instrument at a heating rate of 10 K/min.

Preferred Examples of compounds of the formula (I) are:

-   Compound A-1: 1,3,5-benzenetricarboxylic acid tris(benzylamide);    m.p.=243° C.-   Compound A-2: 1,3,5-benzenetricarboxylic acid    tris(cycloheptylamide); m.p.=394° C.*)-   Compound A-3: 1,3,5-benzenetricarboxylic acid    tris(3-methylcyclohexylamide); m.p.=381° C.*)-   Compound A-4: 1,3,5-benzenetricarboxylic acid    tris(3,4-dimethylphenylamide); m.p.=340° C.**)-   Compound A-5: 1,3,5-benzenetricarboxylic acid    tris(cyclododecylamide); m.p.=393° C.*)-   Compound A-6: 1,3,5-benzenetricarboxylic acid tris(tert-octylamide);    m.p.=315° C.*)-   Compound A-7: 1,3,5-benzenetricarboxylic acid    tris(S(+)-1-cyclohexylethylamide); m.p.=397° C.*)-   Compound A-8: 1,3,5-benzenetricarboxylic acid    tris(R(−)-1-cyclohexylethylamide); m.p.=392° C.*)-   Compound A-9: 1,3,5-benzenetricarboxylic acid tris(cyclooctylamide);    m.p. =402° C.*)-   Compound A-10: 1,3,5-benzenetricarboxylic acid    tris(2,3-dimethylcyclohexylamide); m.p.=418° C.*)-   Compound A-11: 1,3,5-benzenetricarboxylic acid tris(n-butylamide);    m.p.=239° C.    *) Melting under simultaneous evaporation.    **) Melting under decomposition.

The general procedures used in Working Example I are described below.

Mixing Procedure:

To 59.91 g of powdered polypropylene (ELF-Atochem (RTM); Appryl 3030BN1(RTM)) 90 mg of a powdered additive (0.15% by weight) or a powderedmixture of additives (total 0.15% by weight) is added, and tumble-mixedfor 24 h in a glass container. In general, 4.5 g of this mixture arecompounded at 239° C. in a small-scale, laboratory twin-screw,recirculating and corotating extruder, for example the MicroCompounderof DACA Instruments (RTM), for a period of about 4 min at a screw speedof 40 rpm, and subsequently collected at room temperature. The neatpolypropylene is similarly treated to produce a blank control sample.

Differential Scanning Calorimetry (DSC):

A Perkin-Elmer DSC instrument (RTM) (Model DSC 7), operated in a drynitrogen atmosphere, is used for the analysis of the crystallizationbehavior of the various mixtures and control samples, according tostandard procedures. About 5 to 10 mg of sample is sealed into analuminum cup, heated from 130° C. to 230° C. at a rate of 10° C./min,held at 230° C. for 5 min, and then subsequently cooled at a rate of 10°C./min to 50° C. The data represented as crystallization temperaturesare the peak temperatures of the exotherms (predominant peak minimum) inthe thermograms that are recorded upon cooling.

Injection Molding:

The injection molding is performed with a MicroInjector (DACAInstruments (RTM)). About 3.0 g of the pelletized thread is placed undera nitrogen blanket in the barrel at 260° C. After the granulate iscompletely molten, the melt is injected into a polished mold with apressure of about 8 bar. The mold temperature is 20° C. The collectedtest specimen has a diameter of 2.5 cm and a thickness of about 1.1-1.2mm.

Optical Characterization (Transmission, Clarity, Haze):

Transmission, clarity and haze are measured with a haze-gard plusinstrument (BYK, Gardner (RTM), illumination CIE-C) at room temperature.The haze-gard plus instrument conforms to ASTM D-1003. The transmission,clarity and haze values are measured between 12-24 hours after obtainingthe samples by injection molding.

Determination of the β-form Crystal Content by Wide Angle X-rayScattering (WAXS)

A Bruker (RTM) wide angle X-ray diffractometer (Model D8 Advance) isused for the analysis of the β-modification content of the injectionmolded specimen prepared as described above.

The test specimen is placed in a sample holder in the middle between thecopper K_(α) radiation source (γ=1.54178 Å) and the detector. The sampleis placed in a position so that the machine direction (MD) is parallelto the slit-shaped beam. This position is used for the determination ofthe β-form crystal content. The diffraction pattern is recorded from 2Θ=8−30°. The β-form crystal content is determined as described by A.Turner Jones et al., Makromol. Chem. 75, 134 (1964) and in U.S. Pat. No.5,491,188 according to the following equation:β-form crystal content (%)=100×P ₆₂ ₁/(P _(α1) +P _(α2) +P _(α3) +P_(β1))where P_(α1) to P_(α3) means the maximum peak heights of the α-form andP_(β1) means the maximum peak height of the β-form determined by wideangle X-ray scattering.

-   P_(β1) is a reflection intensity (height) on (300) plane of β-form    crystal.-   P_(β1) is a reflection intensity (height) on (110) plane of α-form    crystal.-   P_(α2) is a reflection intensity (height) on (040) plane of α-form    crystal.-   P_(α3) is a reflection intensity (height) on (130) plane of α-form    crystal.

EXAMPLE I

0.15 wt % of the compound indicated in Table 1 are added to thepolypropylene resin, processed and characterized according to the abovemethods.

The transmission, haze, clarity, recrystallization temperature and theβ-form crystal content of the polypropylene composition according to thepresent invention are listed in Table 1 as well as the thickness of thetest specimen (plate).

TABLE 1 The recrystallization temperature (T_(cr)) of the polypropyleneresin without β-nucleating agent: 112.0° C. Thickness of theβ-nucleating Transmission β-form crystal plate in agent in % Haze in %Clarity in % ¹⁾T* in ° C. content in % mm A-1 85.7 75.2 87.6 120.0 151.12 A-2 86.7 71.7 91.2 123.3 29 1.11 A-3 88.3 96.1 84.0 120.5 37 1.12A-4 83.0 92.8 90.3 116.1 38 1.12 A-5 88.1 87.0 91.7 122.1 38 1.11 A-688.8 35.8 98.9 124.3 40 1.11 A-7 87.5 90.2 90.4 125.7 45 1.15 A-8 88.572.7 98.0 124.8 59 1.16 A-9 82.4 97.6 83.3 124.3 64 1.13 A-10 86.2 98.272.3 121.6 74 1.13 ¹⁾T*: Recrystallization temperature of thepolypropylene resin containing the β-nucleating agent.

EXAMPLE II

2.5 kg of polypropylene powder (Moplen FL F 20 (RTM) of Montell (RTM))are mixed to homogeneity in a high-speed mixer with 0.10% oftris(2,4-di-tert-butylphenyl)phosphite, 0.05% of pentaerythritoltetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyi)propionate, 0.10% ofcalcium stearate and 0.20% of Compound A-10. This blend is then extrudedin a twin-screw extruder of Berstorif (RTM) at a temperature of at most240° C. After drawing the extrudate through a waterbath to cool, it isgranulated.

Injection Molding (Example IIa):

90 mm×85 mm×2 mm test panels are moulded from these granules by means ofan injection-moulding machine (Arburg 320 S (RTM)) at a temperature ofat most 240° C. (mold temperature 50° C.).

Compression Molding (Examples IIb to IIf):

140 mm×240 mm×2 mm thick test panels are compression molded from thesegranules.

EXAMPLE IIb

55 g of the granules are molten at T₁=240° C. for 15 min in a melt pressSuter LP 322 (RTM). Subsequently, the molten polypropylene resincomposition is put in a second melt press (Suter LP 322 (RTM)) which hasa temperature of T₂=60° C. The samples are pressed at p=10 bar and areannealed/crystallized for 5 min.

EXAMPLE IIc

55 g of the granules are molten at T₁=240° C. for 15 min in a melt pressSuter LP 322 (RTM). Subsequently, the molten polypropylene resincomposition is put in a second melt press (Suter LP 322 (RTM)) which hasa temperature of T₂=80° C. The samples are pressed at p=10 bar and areannealed/crystallized for 10 min.

EXAMPLE IId

55 g of the granules were molten at T₁=240° C. for 15 min in a meltpress Suter LP 322 (RTM). Subsequently, the molten polypropylene resincomposition is put in a second melt press (Suter LP 322 (RTM)) which hasa temperature of T₂=100° C. The samples are pressed at p=10 bar and areannealed/crystallized for 30 min.

EXAMPLE IIe

55 g of the granules are molten at T₁=240° C. for 15 min in a melt pressSuter LP 322 (RTM). Subsequently, the molten polypropylene resincomposition is put in a second melt press (Suter LP 322 (RTM)) which hasa temperature of T₂=110° C. The samples are pressed at p=10 bar and areannealed/crystallized for 60 min.

EXAMPLE IIf

55 g of the granules are molten at T₁=240° C. for 15 min in a melt pressSuter LP 322 (RTM). Subsequently, the molten polypropylene resincomposition is put in a second melt press (Suter LP 322 (RTM)) which hasa temperature of T₂=120° C. The samples are pressed at p=10 bar and areannealed/crystallized for 120 min.

The β-form crystal content of the samples is determined by Wide AngleX-ray Scattering (WAXS) and the recrystallization temperature isdetermined by Differential Scanning Calorimetry (DSC) as describedbelow. The results are listed in Table 2.

WAXS:

A Siemens (RTM) wide angle X-ray diffractometer (Model D500) is used forthe analysis of the β-modification content of the specimen prepared asdescribed above. The test specimen is placed in a sample holder in themiddle between the copper K_(α) radiation source (γ=1.54178 Å) and thedetector. The sample is rotated during the recording at 2 rpm. Thediffraction pattern is recorded from 2Θ=5-35° at an increment of 0.0250and a recording time of 1 sec. The β-form crystal content is determinedas described under Example I.

DSC:

A TA Instruments (RTM) DSC apparatus (Model DSC 2920 Modulated DSC),operated in a dry nitrogen atmosphere, is used for the analysis of thecrystallization behavior of the various mixtures and control samples,according to standard procedures. About 5 to 10 mg of sample is sealedinto an aluminum cup, heated from ambient temperature to 240° C. at arate of 10 K/min, held at 240° C. for 5 min, and then subsequentlycooled at a rate of 10 K/min to ambient temperature. The datarepresented as crystallization temperatures are the peak temperatures ofthe exotherms (predominant peak minimum) in the thermograms that arerecorded upon cooling.

TABLE 2 Recrystallization temperature (T_(cr)) of the polypropyleneresin (component (1)) without β-nucleating agent: 109.0° C.Recrystallization temperature (T*) of the polypropylene resin containing0.20% by weight of Compound A-10: 124.1° C. Example β-nucleating agentT_(s) in ° C. β-form crystal content in % II-a A-10 50 58 II-b A-10 6068 II-c A-10 80 66 II-d A-10 100 47 II-e A-10 110 44 II-f A-10 120 33

EXAMPLE III

Compounding:

5 kg of polypropylene homopolymer (Moplen (RTM) PH 350 (RTM) of Montell(RTM)) powder are mixed to homogeneity in a high-speed mixer with 0.10%of tris(2,4-di-tert-butylphenyl)phosphite, 0.05% of pentaerythritoltetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 0.10% ofcalcium stearate and different amounts of Compound A-10 (0.025, 0.05 or0.1% by weight, relative to the weight of the polypropylene homopolymerpowder). This blend is then extruded in a twin-screw extruder ofBerstorff (RTM) (screw diameter 25 mm, L/D ratio: 46) at a temperatureof at most 230° C. After drawing the extrudate through a water bath tocool, it is granulated.

Cast Film Preparation:

Cast films are produced by using a single screw extruder (Dr. Collin, E30M) equipped with a cast film line (Dr. Collin CR136/350) attemperatures of 230° C. (extruder) and 115° C. (chill roll). Cast filmsare produced at a thickness of 0.2 mm and 1 mm.

Production of Biaxial Oriented Films:

Test sample preparation: Test samples are cut into 85 mm×85 mm piecesfrom the cast film. Stretching is performed in a biaxial stretchingmachine of Bruckner Karo IV at a Hencky strain of 0.1 s⁻¹ .

-   Initial size L0 (mm): MD×TD=70×70 (clip distance 70 mm)-   Preheating time: 40 sec /150° C.-   Set clip temperature: 95° C.

1. A composition containing (1) a crystalline polypropylene resin and(2) one or more β-nucleating agents of the formula (I),

wherein R₁, R₂ and R₃, independently of one another, are C₁-C₂₀alkyl,C₂-C₂₀alkyl substituted by C₁-C₁₀alkylamino, di(C₁-C₁₀alkyl)amino,C₁-C₁₀alkyloxy or hydroxy; C₃-C₂₀alkenyl, C₅-C₁₂cycloalkyl,C₅-C₁₂cycloalkyl substituted by 1, 2 or 3 C₁-C₁₀alkyl; cyclohexylmethyl;cyclohexylmethyl substituted by 1, 2 or 3 C₁-C₁₀alkyl;C₅-C₉cycloalkenyl, C₅-C₉cycloalkenyl substituted by 1, 2 or 3C₁-C₁₀alkyl; phenyl substituted by 1, 2 or 3 radicals selected from thegroup consisting of C₁-C₁₀alkyl, C₁-C₁₀alkyloxy, hydroxy, halogen,trihalogenmethyl, trihalogenmethoxy, benzoyl, phenylamino, acylamino andphenylazo; C₇-C₉phenylalkyl, C₇-C₉phenylalkyl which is substituted onthe phenyl by 1, 2 or 3 radicals selected from the group consisting ofC₁-C₁₀alkyl, C₁-C₁₀alkoxy and hydroxy; naphthyl, naphthyl substituted byC₁-C₁₀alkyl, adamantyl, or a 5 to 6 membered heterocyclic group;characterized in that the polypropylene resin has a content of β-formcrystals of at least 10% calculated by means of the following equationβ-form crystal content (%)=100×P _(β1)/(P _(α1) +P _(α2) +P _(α3) +P_(β1)) where P_(α1) to P_(α3) are respective peak heights (maxima) ofthe α-form and P_(β1) is a peak height (maximum) of the β-formdetermined by wide angle X-ray scattering.
 2. A composition according toclaim 1, wherein the β-form crystals of component (1) are solidifiedand/or annealed at ambient temperature or at temperatures (T_(S))T _(S) ≦T _(cr)+35° C. T_(cr) being the recrystallization temperature ofthe polypropylene resin (component (1)) without a β-nucleating agent asdetermined by differential scanning calorimetry (DSC) by cooling themolten polypropylene resin at a cooling rate of 10 K/min.
 3. Acomposition according to claim 1 wherein the polypropylene resin ofcomponent (1) has a content of β-form crystals of 10 to 98%.
 4. Acomposition according to claim 1 wherein the polypropylene resin ofcomponent (1) has a content of β-form crystals of 15 to 80%.
 5. Acomposition according to claim 1, which is further characterized in thatthe polypropylene resin has a haze which is greater than 62%; the hazevalue being measured at a plate of 1.1-1.2 mm thickness.
 6. Acomposition according to claim 1 wherein component (1) is apolypropylene homopolymer.
 7. A composition according to claim 1 whereincomponent (1) is a polypropylene random copolymer, alternating orsegmented copolymer or block copolymer containing one or more comonomersselected from the group consisting of ethylene, C₄-C₂₀α-olefin,vinylcyclohexane, vinylcyclohexene, C₄-C₂₀alkanediene,C₅-C₁₂cycloalkandiene and norbornene derivatives.
 8. A compositionaccording to claim 1 wherein component (1) is a thermoplastic polyolefin(TPO).
 9. A composition according to claim 1 which additionally contains(3) a further polymer, with the proviso that component (3) is differentfrom component (1).
 10. A composition according to claim 1 wherein R₁,R₂ and R₃, independently of one another, are C₁-C₂₀alkyl, C₂-C₁₀alkylsubstituted by C₁-C₄alkylamino, di(C₁-C₄alkyl)amino, C₁-C₄alkyloxy orhydroxy; C₃-C₂₀alkenyl, C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkyl substitutedby 1, 2 or 3 C₁-C₄alkyl; cyclohexylmethyl; cyclohexylmethyl substitutedby 1, 2 or 3 C₁-C₄alkyl; phenyl substituted by 1, 2 or 3 radicalsselected from the group consisting of C₁-C₄alkyl, C₁-C₄alkyloxy orhydroxy; benzyl, benzyl which is substituted on the phenyl by 1, 2 or 3radicals selected from the group consisting of C₁-C₄alkyl, C₁-C₄alkoxyand hydroxy; naphthyl, or naphthyl substituted by C₁-C₄alkyl.
 11. Acomposition according to claim 1, wherein R₁, R₂ and R₃, independentlyof one another, are C₁-C₂₀alkyl, C₂-C₆alkyl substituted byC₁-C₄alkylamino, di(C₁-C₄alkyl)amino or C₁-C₄alkyloxy; C₅-C₁₂cycloalkyl,C₅-C₁₂cycloalkyl substituted by 1, 2 or 3 C₁-C₄alkyl; cyclohexylmethyl;cyclohexylmethyl substituted by 1, 2 or 3 C₁-C₄alkyl; phenyl substitutedby 1, 2 or 3 C₁-C₄alkyl; benzyl, benzyl which is substituted on thephenyl by 1, 2 or 3 C₁-C₄alkyl; or naphthyl.
 12. A composition accordingto claim 1 wherein R₁, R₂ and R₃, independently of one another, arebutyl, octyl or octadecyl, 3-dimethylaminopropyl, 3-methoxypropyl or2-methoxyethyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl,3-methylcyclohexyl or 2,3-dimethylcyclohexyl, 1-cyclohexylethyl,3,4-dimethylphenyl, benzyl, or naphthyl.
 13. A composition according toclaim 1 wherein R₁, R₂ and R₃ are identical and are2,3-dimethylcyclohexyl, tert-octyl or cyclooctyl.
 14. A compositionaccording to claim 1 wherein R₁, R₂ and R₃ are identical.
 15. A methodfor providing a polypropylene resin with β-form crystals, whichcomprises incorporating into the polypropylene resin one or moreβ-nucleating agents as defined in claim
 1. 16. A method for providing apolypropylene resin with a content of β-form crystals of at least 10%calculated by means of the following equationβ-form crystal content (%)=100×P _(β1)/(P _(α1) +P _(α2) +P _(α3) +P_(β1)) where P_(α1) to P_(α3) are respective peak heights of the α-form(maxima) and P_(β1) is a peak height (maximum) of the β-form determinedby wide angle X-ray scattering, which comprises incorporating into thepolypropylene resin one or more β-nucleating agents as defined inclaim
 1. 17. A shaped article containing a composition according toclaim
 1. 18. A shaped article according to claim 17, which is a moldedarticle.
 19. A shaped article according to claim 18, where the moldingis effected by injection, blow, compression, roto-molding orslush-molding or extrusion.
 20. A shaped article according to claim 17,which is a film, fiber, profile, pipe, bottle, tank or container.
 21. Amonoaxially-oriented film or a biaxially-oriented film which has beenformed by stretching a film according to claim
 20. 22. A fiber which hasbeen formed by stretching a fiber according to claim
 20. 23. Amultilayer system in which one or more layers contain a compositionaccording to claim
 1. 24. A composition according to claim 1 whichadditionally contains one or more compounds from the group consisting ofphenolic antioxidants, phosphites, phosphonites, phosphonates, dialkylhydroxylamines, nitrones, thiosynergists, benzofuranones, hindered aminelight stabilizers and benzotriazole, benzophenones, acrylate, oxamide ortriazine UV absorbers.